|Publication number||US4898911 A|
|Application number||US 07/137,698|
|Publication date||Feb 6, 1990|
|Filing date||Dec 24, 1987|
|Priority date||Nov 20, 1986|
|Publication number||07137698, 137698, US 4898911 A, US 4898911A, US-A-4898911, US4898911 A, US4898911A|
|Inventors||Shunitsu Miyashita, Kenji Mogami|
|Original Assignee||Kanegafuchi Kagaku Kogyo Kabushiki|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (3), Referenced by (49), Classifications (10), Legal Events (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a continuation-in-part of application Ser. No. 122,738 filed on Nov. 19, 1987.
The present invention relates to a resin composition, and more particularly to a soft resin composition useful for improving the impact resistance of thermoplastic resins, especially thermoplastic resins having ester bonds, carbonate bonds or amido bonds in the molecule.
An improvement in the impact resistance of molded articles of thermoplastic resins has been made generally by blending thermoplastic resins with elastomers. To high performance thermoplastic resins called engineering plastics, this method of blending elastomers has been also applied for the purpose of improving the impact resistance, for instance, as disclosed in Japanese Patent Publication Kokoku No. 58-47419 and No. 59-28223. However, no theory about what elastomers are effective for improving the impact resistance has been established. Also, there are cases where if high performance engineering plastics are blended with elastomers having a relatively low elasticity, the impact resistance is improved, but excellent other properties of engineering plastics such as mechanical strength, heat resistance and chemical properties are impaired. Accordingly, it is the present state that experiments must be repeated by combining the objective engineering plastics with various kinds of elastomeric materials in order to look for the suitable elastomeric materials.
It is an object of the present invention to provide a modifier capable of improving the impact resistance of thermoplastic resins, particularly high performance thermoplastic resins called engineering plastics, without impairing excellent properties that the resins possess such as mechanical strength, heat resistance and chemical properties.
The above and other objects of the present invention will become apparent from the description hereinafter.
It has now been found that a particular resin composition is useful as the modifier for various thermoplastic resins, and when blended with thermoplastic resins, it improves the impact resistance without substantially impairing the properties of the thermoplastic resins.
In accordance with the present invention, there is provided a melt-blended resin composition comprising (a) 5 to 95% by weight of a resin containing at least one epoxy group per molecule and having a modulus of elasticity in bending of at most 104 kg/cm2 at room temperature, and (b) 95 to 5% by weight of a copolymer of an α-olefin and an α,β-unsaturated carboxylic acid wherein at least 5% by mole of the carboxyl groups are neutralized with an alkali metal and which has a modulus of elasticity in bending of at most 104 kg/cm2 at room temperature.
The term "modulus of elasticity in bending" as used herein means the value obtained by dividing the bending stress that a material suffers within the elastic limit by the strain which generates in the material, and it is represented by the unit kg/cm2. The larger the value, the smaller the deformation of material against a constant load.
Polymers containing at least one epoxy group per molecule and having a modulus of elasticity in bending of at most 104 kg/cm2 at room temperature (about 23° C.) are used in the present invention as the component (a). The epoxy group can attach to the polymers in the form of glycidyl ether group, glycidyl ester group, glycidylamino group, or a group derived from a reaction of an N-heterocycle-containing compound and epichlorohydrin as well as epoxy group.
Examples of the epoxy-containing polymer (a) are, for instance, a copolymer of an α-olefin having 2 to 20 carbon atoms and a polymerizable glycidyl compound having 5 to 40 carbon atoms; a copolymer of an alkyl acrylate or methacrylate having a C1 to C36 alkyl group and a polymerizable glycidyl compound having 5 to 40 carbon atoms; a polyolefin to which a glycidyl ether group is introduced such as polyolefins having glycidyl ether group at one or both ends; a graft copolymer of 1 to 90% by weight of methyl acrylate or methacrylate with 99 to 10% by weight of ethylene/glycidyl acrylate or methacrylate; both end epoxidated polybutadiene; epoxidated 1,2-polybutadiene; and the like. All of compounds having α-olefinic group and glycidyl group can be used as the glycidyl compound to be copolymerized with α-olefin or alkyl (meth)acrylate, but usually there are used glycidyl compounds having 6 to 40 carbon atoms, e.g. an α,β-unsaturated carboxylic acid glycidyl ester such as glycidyl acrylate or methacrylate, a glycidyl ether such as allyl glycidyl ether, and a glycidyl group-containing (meth)acrylate oligomer.
Preferable epoxy-containing polymers (a) are copolymers of one or more of α-olefins such as ethylene, propylene, 1-butene, 1-hexene and 1-octene and one or more of α,β-unsaturated caboxylic acid glycidyl esters or polymerizable double bond-containing glycidyl ethers such as glycidyl acrylate, glycidyl methacrylate, cyclohexene-4-carboxylic acid glycidyl ester and allyl glycidyl ether. The copolymers may contain a minor amount of other copolymers may contain a minor amount of other copolymerizable monomers, e.g. at most 10% by weight of other monomers such as vinyl acetate, methyl acrylate or methyl methacrylate. Representative examples of the α-olefin/glycidyl ester or ether copolymers are, for instance, ethylene/glycidyl (meth)acrylate copolymer (e.g. random copolymer of ethylene and glycidyl methacrylate in a ratio of 9:1 by weight having a flow rate of 3.0 g/10 min., or ethylene/glycidyl methacrylate copolymer commercially available under the trade mark "Bondfast" 2C made by Sumitomo Chemical Co., Ltd.), a ternary copolymer of ethylene, glycidyl (meth)acrylate and vinyl acetate (e.g. ethylene/glycidyl methacrylate/vinyl acetate copolymer commercially available under the trade mark "Bondfast" 7B made by Sumitomo Chemical Co., Ltd.), ethylene/propylene/glycidyl methacrylate/vinyl acetate copolymer, and ethylene/allyl glycidyl ether copolymer. The content of the glycidyl ester or ether in the copolymer is preferably from 1 to 30% by weight, especially 5 to 20% by weight. The content of not less than 1% by weight is desirable from the viewpoints of the improvement in impact resistance and the compatibility with thermoplastic resins.
Representative examples of the alkyl (meth)acrylate/glycidyl ester or ether copolymer are, for instance, ethyl acrylate/glycidyl acrylate or methacrylate copolymer and butyl acrylate/allyl glycidyl ether copolymer.
The epoxy-containing polymer is effective for improving the impact resistance of thermoplastic resin molded articles so long as at least one epoxy group is present in the molecule. Preferably, the content of units having epoxy group in the polymer is at least 1% by mole from the viewpoint of the improvement in impact resistance. When the content of the units having epoxy group is more than 10% by mole, the composition of the invention becomes hard and, therefore, the improvement in the impact resistance of molded articles tends to decrease.
Also, the epoxy-containing polymers used in the present invention are those having a modulus of elasticity in bending of at most 10,000 kg/cm2 at room temperature (23° C.). Preferably, the modulus of elasticity in bending is from 100 to 4,000 kg/cm2. The epoxy-containing polymer having a modulus of elasticity in bending of more than 104 kg/cm2 at room temperature should be avoided, since the effect of improving the impact resistance is decreased.
The component (b) used in the present invention is copolymers of α-olefins and α,β-unsaturated carboxylic acids wherein at least 5% by mole of the carboxyl groups are neutralized with an alkali metal. They are known as ionomers. Examples of the α-olefin are, for instance, ethylene, propylene, 1-butene, 1-octene, 1-hexene, and the like. The α-olefin may be used alone or in admixture thereof. Examples of the α,β-unsaturated carboxylic acid are for instance, a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, and a dicarboxylic acid such as maleic acid or fumaric acid. The carboxylic acids may be used alone or in admixture thereof. Preferably, the content of the α-olefin in the ionic copolymer (b) is at least 50% by weight, especially from 50 to 95% by weight.
The copolymer (b) may contain at most 25% by weight, preferably at most 10% by weight, of other copolymerizable monomers, e.g. alkyl (meth)acrylates having a C1 to C10 alkyl group such as methyl acrylate, methyl methacrylate or butyl acrylate.
At least 5% by mole, preferably at least 30% by mole, more preferably at least 50% by mole, of the acid groups are neutralized with an alkali methal such as sodium or potassium. When the degree of neutralization is at least 5% by mole, the impact resistance of thermoplastic resins is greatly improved. This improvement is marked particularly when at least 30% by mole of carboxyl groups are neutralized with sodium ion.
The copolymers (b) used in the present invention are those having a modulus of elasticity in bending of not more than 104 kg/cm2 at room temperature (about 23° C.), preferably 100 to 4,000 kg/cm2. When the modudus of elasticity in bending is more than 10,000 kg/cm2, the impact resistance is not sufficiently improved.
The epoxy-containing polymer (a) and the copolymer (b) are melt-blended in a ratio of 5:95 to 95:5 by weight, preferably 40:60 to 90:10 by weight, more preferably 50:50 to 80:20 by weight, at a temperature of 150° to 280° C., preferably 170° to 200° C., to react them. When the (a)/(b) ratio is outside the above range, the effect of improving the impact resistance of thermoplastic resins is insufficient. When the melt-blending temperature is lower than 150° C., the reaction between the components (a) and (b) does not promptly proceed. Also, if the temperature for blending the components (a) and (b) is higher than 280° C., gellation occurs and the effect of improving the impact resistance is decreased.
When blended with thermoplastic resins, particularly with engineering plastics, the composition of the present invention exerts an excellent effect of improving the impact resistance of the thermoplastic resins. The resin composition (modifier) of the invention is particularly useful for thermoplastic resins containing ester bonds, carbonate bonds or amido bonds in the molecule. Representative examples of the thermoplastic resins to which the modifier of the invention is applicable are, for instance, polyester such as polyethylene terephthalate (PET) or polybutylene terephthalate, polyamide, polycarbonate, polyarylate, (meth)acrylic acid ester polymers, polystyrene, polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymer (ABS), and the like. The modifier of the present invention may be used in combination with other known reinforcing agents or modifiers such as methyl methacrylate-butadiene-styrene copolymer (MBS) and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS). The modifier of the invention is also applicable to fiber glass reinforced thermoplastics and shows a large effect on improvement of impact resistance.
The modifier of the invention is incorporated in thermoplastic resins in an amount such that the ratio of the modifier to the thermoplastic resins is from 5:95 to 50:50 by weight. When the amount of the modifier is less than the above range, the improvement in the impact resistance is insufficient, and even if the modifier is used in an amount larger than the above range, the impact resistance does not raise according to the additional amount of the modifier.
The composition of the present invention may contain usual additives which have been generally used for resin composition, for example, stabilizer, coloring agent, antistatic agent, flame retarder, processing improver, and the like. Further, the composition of the invention may contain a reinforcing material such as glass fiber or carbon fiber, or a filler such as talc, mica, glass beads or calcium carbonate, in an amount of at most 60% by weight.
The composition of the present invention can be incorporated into thermoplastic resins by various known methods, for example, by a method using an extruder.
Molded articles propared from thermoplastic resins incorporated with the resin composition of the invention has an excellent impact resistance and, therefore, can be used suitably as housing for light electrical appliances, automoblie parts, body for power tools, and the like.
The present invention is more specifically described and explained by means of the following Examples in which all parts and % are by weight unless otherwise noted. It is to be understood that the present invention is not limited to the Examples.
There were mixed 75 parts of a copolymer of ethylene and glycidyl methacrylate in a weight ratio of 9:1 having a flow rate of 3.0 g/10 minutes measured according to ASTM D 1238 E (hereinafter referred to as "EGMA") and 25 parts of a random copolymer of 87% of ethylene, 6.5% of methacrylic acid and 6.5% of sodium methacrylate having a melt index of 1.0 g/10 minutes measured according to ASTM D 1238 (hereinafter referred to as "EMANa-1"). The mixture was melt-blended at 205° C. by a biaxial extruder (model PCM-45 made by Ikegai Tekko Kabushiki Kaisha), and extruded.
The extruded composition (modifier) was incorporated in the thermoplastic resin shown in Table 1 by blending using the biaxial exturder at the temperature shown in Table 1. The obtained extrudate was injection-molded to give test specimens, and the impact resistance was evaluated according to the following methods.
The results are shown in Table 1.
Also, the modifiers obtained in Examples 1 to 3 were extracted with xylene for 10 hours under reflux. In each case, the amount of eluted matter from the modifier was less than 5%.
The modulus of elasticity in bending of the components (a) and (b) was measured according to ASTM D 790.
Measurement was made according to ASTM D 256.
The test was made with respect to specimens having a thickness of 3 mm using an egg apple type weigth of 500 g in weight and 3/8 inch in top portion radius R. The 50% failure height (the height which causes the failure of 50% of the number of test pieces tested) is shown in the table.
To 100 parts of the composition (modifier) shown in Table 1 were added 0.2 part of a stabilizer (commercially available under the trade mark "Irganox" 1010 made by Ciba-Geigy AG.) and 0.2 part of a stabilizer (commercially available under the trade mark "Seanox" 412S made by Shipro Kasei Kaisha Co.). The mixture was melt-blended and extruded, and then was incorporated in polyethylene terephthalate by using an extruder. The resulting blend was dried at 80° C. for 24 hours under vacuum, and was injection-molded to give test specimens.
The results are shown in Table 1.
The procedure of each of Examples 2, 4 and 5 was repeated except that the component (a), the component (b) and the thermoplastic resin were simultaneously blended instead of blending the thermoplastic resin with the modifier consisting of the components (a) and (b).
The results are shown in Table 1.
TABLE 1__________________________________________________________________________ Degree of neutralization Modulus of elasticity of carboxyl groups Temperature ofModifier (weight ratio) in bending (kg/cm2) Na in component melt-blendingComponent (a) Component (b) Component (a) Component (b) (% by mole) (a) and__________________________________________________________________________ (b)Ex. 1EGMA*1 75 EMANa-1*4 25 900 3900 50.0 205° C.Ex. 2EGMA 75 EMANa-1 25 900 3900 50.0 205° C.Ex. 3EGMA 75 EMANa-1 25 900 3900 50.0 205° C.Ex. 4BA-AGE*2 50 EMANa-2*5 50 1000 3800 28.6 180° C.Ex. 5E-GMA-VA*3 67 EMANa-2 33 300 3800 28.6 197° C.Com. EGMA 75 EMANa-1 25 900 3900 50.0 --Ex. 1Com. BA-AGE 50 EMANa-2 50 1000 3800 28.6 --Ex. 2Com. E-GMA-VA 67 EMANa-2 33 300 3800 28.6 --Ex. 3__________________________________________________________________________Composition of test specimen (%) Temperature of Izod impact Falling weight Thermoplastic resin blending (a), (b) and strength (notched) impactModifier Kind Amount Glass fiber*10 thermoplastic resin (kg · cm/cm) strength__________________________________________________________________________ (cm)Ex. 115 PC*6 70 15 270° C. 16.0 20Ex. 230 PET-1*7 40 30 280° C. 21.0 42Ex. 320 PA*8 40 40 270° C. 17.8 44Ex. 440 PET-2*9 60 -- 280° C. 31.1 >75Ex. 530 PET-2 35 35 280° C. 28.4 55Com. 30 PET-1 40 30 280° C. 16.5 31Ex. 1Com. 40 PET-2 60 -- 280° C. 25.8 >75Ex. 2Com. 30 PET-2 35 35 280° C. 21.0 42Ex. 3__________________________________________________________________________(Notes)*1 EGMA: Ethylene/glycidyl methacrylate copolymer (9/1 by weight,flow rate 3.0 g/10 min.)*2 BA-AGE: Butyl acrylate/allyl glycidyl ether copolymer having aMooney viscosity of 30 (allylglycidyl ether content: 4.5%)*3 E-GMA-VA: Ethylene/glycidyl methacrylate/vinyl acetate copolymer(85/10/5 by weight) having a meltindex of 7 g/10 min. (ASTM D-1238)*4 EMANa-1: Random copolymer of 87% of ethylene, 6.5% of methacrylicacid and 6.5% of methacrylicacid sodium salt having an MI of 1.0 g/10 min. (ASTM D-1238)*5 EMANa-2: Random copolymer of about 86% of ethylene, about 10% ofmethacrylic acid and about 4%of methacrylic acid sodium salt having an MI of 2.8 g/10 min. (ASTMD-1238)*6 PC: Polycarbonate (trade mark "Panlite", product of TeijinLimited)*7 PET-1: Modified polyethylene terephthalate having an intrinsicviscosity of 0.60 (in phenol/1,1,2,2-tetrachloroethane = 1/1 by weight at 25° C.) wherein 65% of apolyethylene terephthalatoligomer is copolymerized with 35% of an addition polymerization productof ethyleneoxide with polypropylene glycol (trade mark "Nissan Unilub" 20DP/15B madeby Nippon Oil andFats Co., Ltd., ethylene oxide/propylene oxide = 20/80 by weight, averagemolecular weight1,300)*8 PA: Polyamide (trade mark "Alamin" CM 1017 made by TorayIndustries, Inc.)*9 PET-2: Modified polyethylene terephthalate having intrinsicviscosity of 0.60 (in phenol/1,1,2,2-tetrachloroethane = 1/1 by weight at 25° C.) wherein 90% of apolyethylene terephthalateoligomer (pentamer) was copolymerized with 10% of a bisphenol A-ethyleneoxide additionpolymerization product having an average molecular weight of 1,000 bymelt-blending themunder reduced pressure*10 Glass fiber: commercially available under the trade mark"Glasslon" 03JA-429 made by AsahiFiber Glass Kabushiki Kaisha
From the results shown in Table 1, it would be apparent that the resin composition of the present invention prepared by melt-blending the epoxy-containing polymer (a) and the ionomer (b) imparts an excellent impact resistance to thermoplastic resins.
In addition to the ingredients used in the Examples, other ingredients can be used in the Examples as set forth in the specification to obtain substantially the same results.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4659757 *||Mar 7, 1986||Apr 21, 1987||Unitika Ltd.||Polyester resin composition for forming an impact resistant article|
|JPS59115352A *||Title not available|
|JPS59184251A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4968752 *||Jan 29, 1990||Nov 6, 1990||Du Pont-Mitsui Polychemicals Co., Ltd.||Ionomer composition|
|US5336701 *||Sep 28, 1992||Aug 9, 1994||General Electric Company||Process improvement for improved color reduced gloss thermoplastic compositions|
|US5508347 *||Jun 15, 1994||Apr 16, 1996||Sumitomo Chemical Company, Limited||Delustered amorphous thermoplastic resin composition|
|US5536780 *||Aug 20, 1993||Jul 16, 1996||General Electric Company||Process for the manufacture of low gloss resins|
|US5543467 *||Jun 29, 1994||Aug 6, 1996||Sumitomo Rubber Industries, Ltd.||Golf ball|
|US5580924 *||Feb 23, 1993||Dec 3, 1996||General Electric Company||Reduced gloss thermoplastic compositions and processes for making thereof|
|US5623018 *||Jun 7, 1995||Apr 22, 1997||Sumitomo Chemical Company, Ltd.||Thermoplastic resin composition including an amorphous resin, an epoxy group-containing ethylene copolymer, and a polyfunctional compound or a carboxylic acid metal salt|
|US5625003 *||Feb 16, 1993||Apr 29, 1997||Sumitomo Rubber Industries, Ltd.||Golf ball|
|US6136920 *||Feb 24, 1995||Oct 24, 2000||Elf Atochem S.A.||Multiphase thermoplastic compositions|
|US6407164||May 20, 1996||Jun 18, 2002||Atofina Sa||Multiphase thermoplastic compositions|
|US7189787||Apr 2, 2004||Mar 13, 2007||Valspar Sourcing, Inc.||Aqueous dispersions and coatings|
|US7439001||Aug 18, 2005||Oct 21, 2008||International Business Machines Corporation||Focus blur measurement and control method|
|US7592047||Oct 18, 2005||Sep 22, 2009||Valspar Sourcing, Inc.||Coating compositions for cans and methods of coating|
|US8092876||Jul 17, 2009||Jan 10, 2012||Valspar Sourcing, Inc.||Coating compositions for cans and methods of coating|
|US8142868||Mar 27, 2012||Valspar Sourcing, Inc.||Coating compositions for cans and methods of coating|
|US8173265||May 8, 2012||Valspar Sourcing, Inc.||Coating compositions for cans and methods of coating|
|US8465846||Jun 18, 2013||Valspar Sourcing, Inc.||Aqueous dispersions and coatings|
|US8617663||Mar 5, 2012||Dec 31, 2013||Valspar Sourcing, Inc.||Coating compositions for cans and methods of coating|
|US8747979||Jul 16, 2010||Jun 10, 2014||Valspar Sourcing, Inc.||Coating compositions and articles coated therewith|
|US8840966||Sep 17, 2010||Sep 23, 2014||Valspar Sourcing, Inc.||Polyurethane coating composition|
|US8911874||Jan 7, 2014||Dec 16, 2014||Valspar Sourcing, Inc.||Aqueous dispersions and coatings|
|US9011999||Sep 17, 2010||Apr 21, 2015||Valspar Sourcing, Inc.||Coating composition including an unsaturated polymer|
|US9029470||Feb 22, 2010||May 12, 2015||Akzo Nobel Coatings International B.V.||Latex emulsions and coating compositions formed from latex emulsions|
|US9061798||Apr 29, 2014||Jun 23, 2015||Valspar Sourcing, Inc.||Coating composition and articles coated therewith|
|US9097989||Jan 27, 2009||Aug 4, 2015||International Business Machines Corporation||Target and method for mask-to-wafer CD, pattern placement and overlay measurement and control|
|US9206332||Mar 17, 2015||Dec 8, 2015||Valspar Sourcing, Inc.||Coating composition including an unsaturated polymer|
|US9394456||May 15, 2014||Jul 19, 2016||Akzo Nobel Coatings International B.V.||Latex emulsions and coating compositions formed from latex emulsions|
|US20040259989 *||Apr 2, 2004||Dec 23, 2004||O'brien Robert M.||Aqueous dispersions and coatings|
|US20060100366 *||Oct 18, 2005||May 11, 2006||O'brien Robert M||Coating compositions for cans and methods of coating|
|US20070041003 *||Aug 18, 2005||Feb 22, 2007||International Business Machines Corporation||Focus blur measurement and control method|
|US20070058169 *||Sep 13, 2005||Mar 15, 2007||International Business Machines Corporation||Multi-layer Alignment and Overlay Target and Measurement Method|
|US20070117928 *||Jan 18, 2007||May 24, 2007||Valspar Sourcing, Inc.||Aqueous Dispersions and Coatings|
|US20080026298 *||Jul 31, 2006||Jan 31, 2008||International Business Machines Corporation||Method to optimize grating test pattern for lithography monitoring and control|
|US20080144031 *||Feb 6, 2008||Jun 19, 2008||International Business Machines Corporation||Overlay target and measurement method using reference and sub-grids|
|US20080259334 *||Jun 23, 2008||Oct 23, 2008||International Business Machines Corporation||Multi layer alignment and overlay target and measurement method|
|US20090011342 *||Sep 15, 2008||Jan 8, 2009||International Business Machines Corporation||Method to optimize grating test pattern for lithography monitoring and control|
|US20090011346 *||Sep 15, 2008||Jan 8, 2009||International Business Machines Corporation||Focus blur measurement and control method|
|US20090186286 *||Jul 23, 2009||International Business Machines Corporation||Method To Control Semiconductor Device Overlay Using Post Etch Image Metrology|
|US20100075084 *||Mar 25, 2010||Valspar Sourcing, Inc.||Coating Compositions for Cans and Methods of Coating|
|US20100183835 *||Jul 22, 2010||Valspar Sourcing, Inc.||Coating Compositions for Cans and Methods of Coating|
|US20110012563 *||Jan 20, 2011||Anil Paryani||Fast charging of battery using adjustable voltage control|
|US20110014533 *||Jul 14, 2009||Jan 20, 2011||Ford Global Technologies, Llc||Method and system for power control in an automotive vehicle|
|US20110058170 *||Nov 9, 2010||Mar 10, 2011||International Business Machines Corporation||Multi layer alignment and overlay target and measurement method|
|US20110069314 *||Mar 24, 2011||International Business Machines Corporation||Multilayer alignment and overlay target and measurement method|
|US20110195213 *||Aug 11, 2011||Valspar Sourcing, Inc.||Aqueous Dispersions and Coatings|
|CN100412114C||Apr 2, 2004||Aug 20, 2008||瓦尔斯帕供应公司||Aqueous dispersions and coatings|
|EP0488119A2 *||Nov 25, 1991||Jun 3, 1992||Nippon Petrochemicals Company, Limited||Mouldable thermoplastic resin composition|
|EP0611090A1 *||Feb 2, 1994||Aug 17, 1994||General Electric Company||Core-shell ABS copolymers|
|WO2004090020A1 *||Apr 2, 2004||Oct 21, 2004||Valspar Sourcing, Inc.||Aqueous dispersions and coatings|
|U.S. Classification||525/74, 525/208, 525/72, 525/201|
|International Classification||C08L23/02, C08G81/02|
|Cooperative Classification||C08G81/021, C08L23/025|
|European Classification||C08L23/02D, C08G81/02D|
|Dec 24, 1987||AS||Assignment|
Owner name: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA, 2-4, NA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:MIYASHITA, SHUNITSU;MOGAMI, KENJI;REEL/FRAME:004809/0227
Effective date: 19871216
Owner name: KANEGAFUCHI KAGAKU KOGYO KABUSHIKI KAISHA,JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MIYASHITA, SHUNITSU;MOGAMI, KENJI;REEL/FRAME:004809/0227
Effective date: 19871216
|Jun 18, 1991||CC||Certificate of correction|
|Jul 23, 1993||FPAY||Fee payment|
Year of fee payment: 4
|Sep 16, 1997||REMI||Maintenance fee reminder mailed|
|Feb 8, 1998||LAPS||Lapse for failure to pay maintenance fees|
|Apr 21, 1998||FP||Expired due to failure to pay maintenance fee|
Effective date: 19980211